XRD Lecture LH
XRD Lecture LH
XRD Lecture LH
Laura Holz
[email protected]
2023
What is an X-ray?
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How are X-ray produced
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How are X-ray produced
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Bragg’s Law
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Bragg’s Law
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Bragg’s Law
x z
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Fundamentals
} X-Ray Diffraction on Crystals
v Bragg’s Law
2 dhkl sin q = n l
dhkl - interplanar spacing of the crystal
q - angle of incidence
l - wavelength of the incident X-RAY
n - order of reflection (integer)
v For parallel planes of atoms with a dhkl between the planes, constructive interference only
occurs when Bragg’s law is satisfied
• In most diffractometers, the X-ray wavelength l is fixed
• A family of planes production a diffraction peak only at a specific angle q
v Additionally, the plane normal [hkl] must be parallel to the diffraction vector
• Plane normal [hkl]: the direction perpendicular to a plane of atoms
• Diffraction vector s: the vector that bisects the angle between the incident and diffracted beam
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X-Ray Diffractometer
} Bragg-Brentano configuration (reflection)
v The incident angle w is defined between the X-ray source and the sample.
v The diffraction angle 2q is defined beween the incident beam and the detector
• In a q: 2q instrument (e.g. Rigaku H3R) the tube is fixed, the sample rotates at q°/min and the
detector rotate at 2q°/min
• In a q: q instrument (e.g. PANanalytical X’Pert Pro) the sample is fixed and the tube rotates at a
rate -q °/min and the detector rotates at a rate of q °/mi
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Primary Optics
1)Soller Slits
• Corrects Angular Divergence
2) Divergence Slits
• Controls beam spread
3) Monochromator
• Absorbs Kβ radiation and white radiation
• Allows Kα1 and Kα2 through
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Secondary Optics
1)Selection Slit
• Reduce scattering of x-rays amorphous or
air scattering
3) Receiving Slit
• Remove diffuse scattered x-rays
4) Secondary Monochromator
• Absorbs Kβ radiation and white radiation
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X-Ray Diffractometer
} Bragg-Brentano configuration (reflection)
v A polycrystalline sample should contain thousands of crystallites. Therefore, all possible
diffraction peaks should be observed
v For every set of planes, there will be a small percentage of crystallites that are properly oriented to
diffract (the plane perpendicular bisects the incident and difracted beams)
v Basic assumptions of powder difrfraction are that for every set of planes there are an equal number of
crystallies that will diffract and that there is a statistically relevant number of crystallites
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X-Ray Powder Diffraction
} Samples
v Samples can be powders, sintered pellets, metal foils, coatings on substrates
v The ideal powder sample contains tens of thousands of randomly oriented crystallites
• Every diffraction peak is the product of X-rays scattering from an equal number of crystallites
• Only a small fraction of the crystallites in the specimen actually contribute to the measured diffraction pattern
v Irradiating a larger volume of material can help ensure that a statistically relevant number of grains
contribute to the diffraction pattern
v Small sample quantities should be avoid because the sample size limits the number of crystallites that
can contribute to the measurement
v If the crystallites in a sample are very large there will not be a smooth distribution of crystal
orientations. Crystallites should be < 10 µm in size to get good powder statistics
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X-Ray Powder Diffraction
} Difractogram: powder diffraction data are collected as Absolute Intensity vs 2q
v The peak position as 2q depends on instrumental characteristic such as wavelength, l
• The peak position as dhkl is an intrinsic, instrument-independent, material property.
® Bragg’s Law is used to convert observed 2q to dhkl
v The absolute intensity, i.e, number of X-rays observed in a given peak, can vary due to instrumental and
experimental parameters
• The relative intensities of the difraction peaks should be instrument independent
® To calculate relative intensity, divide the absolute intensity of every peak by the absolute intensity of the most intense peak,
and then convert to a percentage. The most intense peak of a phase is therefore called the “100 % peak”
® Peak areas are much more reliable than peaks heights as a measure of intensity.
Raw Data Peak List and Parameters
Position Intensity
(2-theta) (counts) No Pos. d-spacing Rel. Int. FWHM Area Backgr. Height
10 154 . [°2Th.] [Å] [%] [°2Th.] [cts*°2Th.] [cts] [cts]
10.02 144 1 21.2986 4.1718 1.21 0.1574 13.9 139 89.51
10.04 149 2 30.2359 2.95597 100 0.1968 1436.41 169 7399.07
10.06 144 3 37.1856 2.41794 6.74 0.1574 77.5 164 499
10.08 154 4 43.2608 2.09143 32.64 0.1771 421.93 178 2414.87
10.1 114 5 48.6052 1.87323 0.75 0.2362 12.85 170 55.15
10.12 125 6 53.595 1.71001 38.99 0.1378 392.03 185 2884.81
10.14 121 7 62.681 1.48099 15.64 0.096 148.1 178 1157.07
10.16 149 8 67.1279 1.39443 0.22 0.9446 15.24 169.4 16.36
10.18 149 9 71.1381 1.32426 14.25 0.168 236.1 174 1054.02
10.2 135 10 75.1653 1.26298 1.33 0.192 25.26 173 98.68
······· ······ 11 79.1815 1.20869 4.02 0.24 95.28 174 297.74
······· ······· 12 79.4331 1.20849 2.33 0.144 33.16 174 172.73
Difractogram of a powder sample of BaZrO3
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X-Ray Powder Diffraction
Peak Position
Determined by size and symmetry of unit
} Information Provided From the Difractogram cell
Peak Width
Influenced by size/strain of crystallites – the
microstruture
Peak Intensities:
Determined by the position of the atoms in
the unit cell; influenced by preferred
orientation
Peak Tails
Diffuse scattering, point defects
Background
Amorphous contents
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X-Ray Powder Diffraction
} Information Provided From the Difractogram
v Identification of phases
• Unit cell latice parameters and Bravais lattice symmetry
® Index peak positions
® Lattice parameters can vary as a function of, and therefore give you information about alloying,
doping, solid solutions, strains
v Crystal Structure
• By Rietveld refinement of the entuire diffraction pattern. Determines the relative amounts of phases in a mixture by
refering the relative peak intesities
v Other defects (e.g. stacking faults) can be measured by analysis of peak shape and peak width
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X-Ray Powder Diffraction
} Phase identification
v The diffraction pattern for every phase is as unique as your fingerprint
• Phases with the same chemical composition can have different diffraction patterns
• The position and relative intensity of a series of peaks to match experimental data to the reference
patterns in the database
monoclinic
tetragonal
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X-Ray Powder Diffraction
} Phase identification Same element. Different allotropes
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Crystal structure determination
Simple Cubic (SC) Body Centred Cubic (BCC) Face Centred Cubic (FCC)
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Crystal Structure determination
Selection rules
(hkl) (h2+k2+l2) SC BCC FCC
100 1 ü û h+k+l = û h,k,l all
110 2 ü ü even û even or
111 3 ü û ü all odd
200 4 ü ü ü
210 5 ü û û
211 6 ü ü û
220 8 ü ü ü
300 9 ü û û
310 10 ü ü û
311 11 ü û ü
222 12 ü ü ü
320 13 ü û û
321 14 ü ü û
400 16 ü ü ü
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Crystal Structure determination
2q
44.48
51.83
76.35
92.90
98.40
121.87
144.54
155.51
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How to guide!
l= 2dsinq (1)
l2/4a2 = sin2q/(h2+k2+l2)
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How to guide! l2/4a2 = sin2q/(h2+k2+l2)
Systematic absences?
ü
FCC = hkl all odd or all even
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How to guide!
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X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
® Crystallite Size
® Microstrain
o Non-uniform Lattice Distortions
o Faulting
o Dislocations
o Antiphase Domain Boundaries
o Grain Surface Relaxation
® Solid Solution Inhomogeneity
® Temperature Factors
• Instrumental broadening (also referred as the Instrumental Profile, Instrumental Peak Profile)
® depend on source and equipment
• Peak width (B) is inversely proportional to crystallite size and cos (q)
® As the crystallite size gets smaller, the peak gets broader
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X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation
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X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation
• Scherrer Constant, K
® depends on the how the width is determined, the shape of the crystal and the size
distribution
Ä K actually varies from 0.62 to 2.08
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X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation
Information
Peak Fit Functions
from fit:
• Position • Gaussian
• Width
• Height • Lorentzian
• Area
• Pearson-VII
• Deconvolution
• Skewness (sharp peaks)
• Pseudo-Voight
(round peaks)
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X-Ray Powder Diffraction
} Estimation of Crystallite Size
v Scherrer Equation
® There is only broadening due to crystallite size when the crystallite is too small to be
® The minimum size requires enough repeating atomic planes to produce the
diffraction phenomenon
Ä this depends on the size of the unit cell
Ä the minimum size is typically between 3 to 10 nm, depending on the material
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X-ray Powder Diffraction
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X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot
• Microstrain Broadening
® Lattice strains from displacements of the unit cell about their normal
positions
® Microstrains are very comon in nanoparticles materials
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X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot
• Microstrain Broadening
distortion
® Contributions to Microstrain Broadening planes
Ä Dislocations
Ä Antiphase Domain Boundaries
Ä Grain Surface Relaxation
® The peak broadening due to microstrain will
vary as:
- strain
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X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot
• When both crystallite size and microstrain are present, a Williamson-Hall Plot is used
Size Broadening
Microstrain Broadening
! l
Bspecimen cosq = + " e #sinq
L
slope
y-intercept
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X-Ray Powder Diffraction
} Estimation of Crystallite Size and Microstrain
v Williamson-Hall Plot
! l
Bspecimen cosq = + " e #sinq
L
slope
y-intercept
Peak Fitting
0.003
Pos. [°2Th.] d-spacing [Å] Rel. Int. [%] FWHM [°2Th.] L = 96 nm
30.1938 2.95755 100 0.1903 e = 0.03
0.001
38 0.2 0.3 0.4 0.5 0.6 0.7
sinq
X-Ray Powder Diffraction
} Advantages
v Only a small quantity of material is required, particularly if the camera method is used.
v The actual chemical compounds are determined. Most methods of analysis only give the
elements present, so it is not always possible to state the compounds present.
v Analysis of difractograms of the sample can also information about the presence of
amorphous materials or the existence of prefered orientation
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X-Ray Powder Diffraction
} Limitations
v It is not possible to identify:
• Non crystalline (amorphous) materials
• Components in a mixture ocurring bellow about 0.5% by weight since there would be
insufficient of the materials present to give measurable diffraction lines.
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End
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